Process of spinning viscose



Patented May 20, 1941 UNITED, STATES PATENT OFFICE PROCESS OF SPINNING VISCOSE Rudolph S. Bley, Elizabethton, Tenn., assignor to North American Rayon Corporation, New York,

In the manufacture of cellulosic products, such as filaments, threads, and the like, a viscose solution is continuously extruded through the minute orifices of a spinneret into a coagulating or setting bath. However, since the introduction of the viscose process great troubles have been and are still experienced as far as continuous spinning is concerned due to impurities, such as, for example, precipitated cellulose particles, sulphur and resin particles, zinc compounds, etc., present in either the viscose solution or the spin bath. These impurities gradually contaminate the spinnerets, clog and reduce with a tertiary base selected from the group consisting of amines, phosphines, arsines and stibines, or with an organic sulphide selected from the group consisting of dialkyl sulphides, diaryl sulphides, and alkyl-aryl sulphides under substantially anhydrous conditions.

Petroleum consists of complex mixtures of hydrocarbons concerning the chemical nature of which there is very little information, although there are indications that all of these materials contain members of the methane series, the polymethylene series and the benzene series of hydrocarbons.v The diiference between petroleums of various sources resides in the proportions of the different types of hydrocarbons and in the chemical nature and amounts of their impurities. Pennsylvania oil, for example, contains a large proportion of methane hydrocarbons and practically no impurities of sulphur or nitrogen compounds. About thirty hydrocarbons have been isolated and identified with certainty. Distillation is the principal method used in separating crude petroleum into useful components. The

distilled fractions from crude petroleum are casinghead gasoline, gasoline, kerosene, gas oil and lighter lubricating oils (neutrals). The residues from such distillation supply most of the lubricating oils ("bright stock"), petrolatum in pasty or liquid form and either paraffin wax or distillate.

petroleum pitch, depending upon the nature of the crude petroleum, Kerosene is any mixture of hydrocarbons which is not volatile enough for use as gasoline in explosion motors. Cracked gasolines are rich in olefins and diolefins. Paraffin wax was originally obtained from tars from the distillation of wood, peat, and lignite, but is now obtained from petroleum, and especially from Pennsylvania paraifin-base oils. Little information is available' about the composition of paraffin waxes except that it consists mainly of higher alkanes and only small amounts of the normal compounds. Petrolatum (Vaseline) is a pasty mixture of hydrocarbons similar to paraflin while liquid petrolatum is a high boiling petroleum Ozokerite is a natural paraffin wax originating in Galicia; in bleached form it is termed ceresin. All of these petroleum hydrocarbons may be halogenated in conventional manner in the presence or absence of catalysts to form halogenated hydrocarbon mixtures adapted to be condensed with the tertiary bases and organic sulphides, set forth above. The hydrocarbonaceous materials 1. e., crude petroleums, casinghead gasolines, gasolines, kerosenes, gas oils, lubricating oils, pasty and liquid petrolatums and parafiin waxes, to be halogenated may first be dissolved in carbon tetrachloride, etc., and subsequently chlorine, bromine, etc., in gaseous form introduced therein until the heat of reaction abates. Halogenated compounds, containing about 25 to 40% of halogen may be obtained in this manner. However, upon prolonging the introduction of halogens, compounds may be obtained containing up to about of a halogen, and it is to be noted that the boiling or fusing points of the raw materials are either lowered or raised by halogenation. Hydrochloric acid, hydrobromic acid, etc., formed during this reaction must be removed, preferably by neutralization. Catalysts, such as iron, etc., may be added to the mixtures to accelerate halogenation. Halogenation will also proceed more rapidly by carrying out the reaction under the influence of ultra-violet rays. The halogenation may also be performed in accordance with processes disclosed, for example, in U. S. Patent #989,225 to Blakeman of April 11, 1911; U. S. Patent 411,191,916 to Brooks of July 18, 1916; U. S. Patent a l-1,246,810 to Ellis of November 13, 1917; U. S. Patent #1,432,761 to Koch of October 24, 1922; etc". Chlorinated paraffin wax, sold under the trade name 01' Chlorafin is a very suitable raw material for my HD0855.

Tertiary bases, capable of being condensed with the halogenated hydrocarbonaceous materials, set forth above, are for example: Trialkyl amines, dialkyl-aryl amines, alkyl-diaryl amines,

triaryl amines, pyridine, substituted pyridines,

pyridazine, pyrimidine, pyrazine. triasole, oxazole, tetrazole, quinoline, substituted quinolines, acridine, substituted acridines phenanthridines, phenanthrolines, phenazine, picoline, substituted picolines, trialkyl phosphlnes, dialkyl-aryl phosphines, alkyl-diaryl phosphines, triaryl phosphines, trialkyl arsines, dialkyl-aryl arsines, ,alkyl-diaryl arsines, triaryl arsines, trialkyl stibines, dialkyl-aryl stibines, triaryl stibines, etc. Organic sulphides suitable for being condensed with these halogenated petroleum hydrocarbons are dialkyl sulphides, alkyl-aryi sulphides and diaryl sulphides. Thus, during such condensations cation-active ammonium, phosphonium, arsonium, stibonium and sulphonium compounds are obtained which are capable of preventing the incrustation of spinnerets and spinneret holes through which viscose solutions are extruded into a spin bath. These compounds have probably the structure:

r-x-m in which X represents nitrogen, phosphorus, arsenic or antimony, P represents a hydrocarbon chain having 8 or more carbon atoms, and R1, R2 and R: represent aliphatic or aromatic radicals. Cation-active compounds are surface-active compounds which carry in the cation a hydrocarbon chain having eight or more carbon atoms. They are particularly advantageous because they may be used in neutral salt, alkaline and acidic aqueous solutions and also in hard water. In contradistinction to cation-active compounds, anion-active compounds are surfaceactive compounds which carry in the anion a more or less extended hydrocarbon chain. They iiocculate in neutral salt, alkaline and acidic aqueous solutions, and also in hard water. Common soaps, sulphonated oils, etc., are anionactive compounds, and thus they are unable to prevent the incrustation of spinnerets and spinneret holes.

These incrustation inhibitors are prepared by heating a halogenated hydrocarbonaceous material of the group, set forth above, with a tertiary amine or an organic sulphide at a moderate temperature-preferable under refluxuntil condensation is completed. Before heating the two components they may be dissolved in a suitable, inert solvent, such as, for example, benzene, ether, toluene, etc., i. e., in solvents which are incapable of chemically reacting with the compounds to be condensed. The inert solvent may subsequently be removed from the condensation products by distillation and the unreacted base or sulphide separated from the condensation products by distillation, extraction, etc. The crude incrustation inhibitors may contain a number of different condensation products which need not be separated from each other. In other words, the crude condensation products (incrustation inhibitors) containing surface-active and surface-inactive constituents may be added for reasons of economy without further purification to viscose solutions or spin baths (setting baths). Although these cation-active halides, i. e., bromides, chlorides, fluorides and iodides, may form corresponding bases in viscose solutions and salts in spin baths, they retain their surface-activity and, thus, their property of preventing incrustations. If very small amounts of these condensation products are added to viscose soluperimentation. Additions of about 0.4 to 1 gram per liter of viscose solution or spin bath are sumcient to allow continuous spinning without substantially changing the inherent physical characteristics of regenerated cellulose.

Although these cation-active pertroleum derivatives improve the spinning properties of any conventional viscose solution or spin bath, I have found that they are especially valuable as additions to zinc-bearing spin baths, 1. e., spin baths containing a zinc compound, such as, for example, zinc sulphate, these baths having poor spinning qualities.

Example-I About 10 grams of a halogenated petroleum are mixed with about grams of triethanolamine and heated under reflux at a moderate temperature, i. e., a temperature at which the raw materials as well as condensation products formed therefrom remain stable, until condensation is complete. About 0.4 to 1.0 gram of the reddishbrown condensation product is added to one liter of a viscose solution of conventional concentration and maturity. This solution is then extruded into an acid spin bath, such as, for example, a glucose bath, a magnesium-zinc bath, etc. The spinnerets and spinneret holes remain clean on prolonged spinning. Other ammonium as well as phosphonium, arsonium, stibonium and sulphonium compounds, prepared as set forth above, may be used with equal success.

Example I] A conventional viscose solution is extruded through fine orifices in precious metal spinnerets into an acid spin bath, containing sulphuric acid, Sodium sulphate, ammonium sulphate and zinc sulphate and about 0.5% by weight of a cationactive substance prepared by heating (condensing) a chlorinated paraflln or another halogenated hydrocarbonaceous material with pyridine. Spinning irregularities and difficulties are substantially overcome. Without the addition of these incrustation inhibitors, spinning is interrupted after a very short period of time.

Example III The cation-active compound is added to both the viscose solution and the spin bath following Examples I and II.

Although these examples will serve to illustrate the present invention, I do not wish to be limited to the inhibitors and concentrations thereof recited therein, since I may make use of any cation-active ammonium, phosphonium, arsonium, stibonium or sulphonium compound prepared by condensing a halogenated material containing at least one petroleum hydrocarbon enga e having eight or more carbon atoms in its chain selected from the group consisting of crude petroleums, gasolines, kerosenes, lubricating oils, pasty and liquid petrolatums and paraflin waxes with a tertiary amine selected from the group consisting of amines, phosphines, arsines and stibines or an organic sulphide selected from the group consisting of dialkyl sulphides, diaryl sul phides and alkyl-aryl sulphides under substantially anhydrous conditions, provided these cat.- ion-active compounds are sufiiciently soluble in either viscose solutions or spin baths to furnish cations therein.

Modifications of my invention will readily be recognized by those skilled in the art, and I desire to include all such modifications coming within the scope of the appended claims.

I claim:

tion product being sufiiciently soluble-and stable in said bath to become cation-active therein.

7. A spin bath adapted to be used in the manufacture of regenerated cellulose from viscose solutions comprising sulphuric acid, a watersoluble zince compound and about 0.4 to 1.0 gram perv liter of said bath of a cation-active condensation product of a halogenated parafmn wax and a tertiary amine, said condensation product be- 1. A spin bath adapted to be used in the manufacture oi regenerated cellulose from viscose solutions containing about 0.4 to 1.0 gram per liter of a cation-active condensation product of a halogenated hydrocarbonaceous material selected from the group consisting of crude petroleums, gasolines, kerosenes, lubricating oils, pasty petrolatums, liquid petrolatums and paraffin waxes and a tertiary base selected from the group consisting of amines, phosphines, arsines and stibines, said condensation productbeing sufliciently soluble and stable in said bath to become cation-active therein.

2. A spin bath adapted to be used in the manufacture of regenerated cellulose from viscose halogenated paraflin wax and a tertiary phosphine.

4. A spin bath adapted to be used in the manufacture of regenerated cellulose from viscose solutions containing about 0.4 to 1.0 gram per liter of a cation-active condensation product of a halogenated paraflln wax and a tertiary arsine.

5. A spin bath adapted to be used in the manufacture of regenerated cellulose from viscose solutions containing about 0.4 to 1.0 gram per liter of a cation-active condensation product of a chlorinated paraflln wax and triethanolamine.

6. A spin bath, adapted to be used in the manufacture of regenerated cellulose from viscose solutions comprising sulphuric acid, a watersoluble zinc compound and about 0.4 to 1.0 gram per liter of said bath of a cation-active condensation product of a halogenated hydrocarbonaceous material selected from the group consisting of crude petroleums, gasolines, kerosenes, lubricating oils, pasty petrolatums, liquid petrolatums and paraflln waxes and a tertiary base selected from the group consisting of amines. phosphlnes, arsines and stlbines, said condensaing sufliciently soluble and stable in said bath to become cation-active therein.

8. A spin bath adapted to be used in the manufacture of regenerated cellulose from viscose solutions comprising sulphuric acid, a watersoluble zinc compound and about 0.4 to 1.0 gram per liter of said bath of a cation-active condensation product of a halogenated paraflin wax and a tertiary phosphine, said condensation product being sufflciently soluble and stable in said bath to become cation-active therein.

9. A spin bath adapted to be used in the manufacture of regenerated cellulose from viscose solutions comprising sulphuric acid, a water-soluble zinc compound and about 0.4 to 1.0 gram per liter of a cation-active condensation product of a chlorinated paraflin wax and triethanolamine.

10. A spin bath adapted to be used in the manufacture of regenerated cellulose from viscose solutions comprising sulphuric acid, a watersoluble zinc compound and about 0.4 to 1.0 gram per liter of a cation-active condensation product of a halogenated paraflin wax and a tertiary arsine, said condensation product being sufficiently soluble and stable in said bath to become cation-active therein.

11. A spin bath adapted to be used in the manufacture of regenerated cellulose from viscose solutions comprising sulphuric acid, a water-soluble zinc compound and a cation-active condensation product of a halogenated hydrocarbonaceous material selected from the group consisting of crude petroleums, gasolines, kerosenes, lubricating oilsI pasty petrolatums, liquid petrolatums and paraffin waxes and a tertiary base selected from the group consisting of amines, phosphines, arsines and stibines, said condensation product being sufliciently soluble and stable in said bath to become cation-active therein.

12. A spin bath adapted to be used in the manufacture of regenerated cellulose from viscose solutions comprising sulphuric acid, a watermanufacture of regenerated cellulose from viscose solutions comprising sulphuric acid, a watersoluble zinc compound and a cation-active condensation product of a chlorinated paraffin wax and triethanolamine.

RUDOLPH S. BLEY. 

